Di (1, 4 diamino-2-aryl ketone anthraquinone) amides of aromatic dicarboxylic acids



Patented May 27, 1952 UNITED STATES PATENT OFFICE DI 1,4 DIAMINO-Z-ARYII; KETONE "ANTHRAT QUINONE)AMIDES F AROMATIC DICAR- BOXYLIC ACIDS Eduard Moergeli, Neuewelt, near Basel, Switzerland, assignor to Ciba Limited, Basel, Switzer-- land, a Swiss firm N 0 Drawing. v Application J uly,1f7, 1950, Serial No.

174,362; In SlWitzerlaiidiLItilYZZ, 1949 11 Claims? (01. 2s0 207;1.

According to this invention valuable-vat dyestuffs of the anthraquinone series-aremade byreacting two molecular proportions of a l'z4-diaminoanth-raquinonyl-Z-aryl ketone, of" which thalene, diphenyl, pyrene and especially halogen substitution products thereof, such as monochlorobenzene, o-dichlorobenzene, 4-chloro-1:1- diphenyl and also chlorinated naphthalenes, and furthermore other'subs'titution products of benzene and higher aromatic hydrocarbons which are suitable for Friedel-Crafts' reactiom for-example, alkyl benzenes suchas toluene, or alkoxy benzenes such as anisole.

Among the aromatic dicarboxylic acids, of which reactive derivatives,:.especially theacid. chlorides, are reacted-with the aforesaid 'startingr materials in the present process there are' tdbe understood only those of which the carboxyl groups are bound to aromatic nuclei (G-membered carbon rings). The two carboxyl groups may be bound to the same benzene ring. As examples of such mononuclear aromatic dicarboxylic acids there may be mentioned terephthalic acid and isophthalic acid.

It is of special advantage in some cases to use dicarboxylic acids which contain at least two aromatic G-membered rings of which each carries a carboxyl group. These two rings may-be bound together by a simple bond or by a bridge; member. As examples of such dicarboxylic acids:

containing two benzene nuclei bound together dicarboxylic acids containing more highly condensed ring systems such as anthraquinone'-2':6- or -2 :7-dicarboxylic' acid; thianthrene dicarboxylic acids, benzanthrone dicarboxylic acids such as benzanthrone-324:6 or -2:6-dicarboxylic acid? or pyrene',"chry sene"or perylene dicarboxylic acids:

acids'j and especially "fluoran-then'e dicarboxylic The reaction -of-'thereactive derivatives ofsucfl carboxylic acids with" the abovementioned "1 :4- diaminoanthraquinonyl-2-aryl ketones may advantageously be conducted at a raised temperature in an inert high boiling solvent such as mono-, dior tri-chlorobenzene, nitrobenzene or naphthalene, and a catalytically active agent such as a tertiary amine, for example, pyridine or quinoline, may be used in known manner in small quantities or quantities sufficient for binding acid, if desired in combination with other -'ac'i-d-'binding agents.

NHQ (H) wherein R1 and R3 stand for an aryl radical each and wherein COR2- CO stands for the radical of an aromatic dicarboxylic acid of the formula HOOG-Rz-COOH. Theyare's'uitable or dyeing or printing a verywide variety of fibers; especially cellulose fibers such as cotton, linen, and l artificial silk of staple fibers of regenerated cellu'- lose. In this manner there-are obtained valuable tints which are deep and in part covered, and have good uniformity, tinctorial strength, and fastness to light and bucking.

The following examples illustrate the invention; the parts and percentages being by weight unlessotherwise stated and the relationship of parts by weight "to parts by volume being the same as that of: the kilogram to the liter:

EXAMPLE- 1 A 1 mixture l of 1' 32- parts" of fiuor antliene di carboxylic acid? dichloride "of the sam composi' tion: "as-is usedl inr'British "'Patent'No; 533,963} "8 parts? I of 1 :4J=diamino=-Z= paraechlorobenzoylyanthraquinona 5 partsr ea'cht of 'quinoline "and pyridine and 225 parts by volume of 'trichloro 3 4 benzene are heated, while stirring, up to 160 C. EXAMPLE 3 continuously in the course of 3 hours. The whole A mixture f 3.2 parts f 6-]3z 1 benzanthmne is th n st rr d f r a fu t /2 h ur. and the dy dicarboxylic acid, 250 parts by volume of tristufi of the formula chlorobenzene, 15 parts by volume of thionyl HZN which separates in the form of grey needles, is chloride and 0.03 part of quinoline is stirred filtered. It dissolves in concentrated sulfuric in a reflux apparatus first for A hour at 80 C. acid with a yellowish olive coloration, dyes cotand then for a further hour at 120 C'. The ton from an olive-green vat bluish grey tints temperature is further raised slowly, the rewhich are fast to chlorine, boiling and light, and 25 maining 25 parts by volume of solvent are dishas 'a very high tinctorial strength in printing. tilled, and the whole is allowed to cool to 60 C.

. To the mixture, which now contains 6-Bz-1- EXAMPLE 2 benzanthrone dicarboxylic acid dichloride, parts A mixture of 3.2 parts of fluoranthene di of pyridine, 5 parts of quinoline and 8 parts of carboxylic acid dichloride (see British Patent No. 30 1:4-cliamino 2 (para-chlorobenzoyl) anthra 533,963) 8.7 parts of 1:4-diamino-2-(meta-paraquinone are added, and the temperature is raised dichlorobenzoyl) -anthraquinone, parts of in stages to 160 C. in the course of 3 hours. The quinoline and 225 parts of trichlorobenzene is whole is stirred for a further 1%; hours at that slowly heated up to 160 C. in the course of 3 temperature, and then the dyestufi of the formula H N a) C O-NH hours while stirring, and then further stirred is separatedby filtration at about 100 C. It

until the formation of the dyestuff of the followdyes cotton from an olive-green vat very fast ing constitution grey tints.

0 NH, o1 Cm-o 0G0] o O-NH i NH co a NH. f.

is complete. The dyestufi is separated by fil- 7 4 tering while hot washed in turn with trichloro- 0 T A mixture of 2.7 parts of 4:4'-.d1phenylbenzene, alcohol, dilute hydrochloric acid and dicarboxylic i dichloride, 8 parts of 1:441?

water, and dried. It dyes vegetable fibers from a green vat somewhat more bluish grey tints than aKiln-$241991? 9 Obenzoyl) 'anthlanqumone, the dyestufi of Example 1 and likewise yields 5 parts of pyrldme a d 2 parts f tr c o very powerful prints. 1 benzene is treated in'the same way as the mixture described in Example 1. dyestuff of the formula There is obtained the toluene sulfonamide, 22 parts of sodium acetate, and 0.5 part each of copper acetate and euprous tions of the anthraquinone components men- 9 tioned in the following table and one molecular proportion of the acid components given therein can b reacted to produce further dyestufis having the indicated properties. The acid components are used in the form of their acid chlorldes.

chloride is heated While stirring for one hour at 170-175 C, The reaction product is poured into Water and the water-soluble constituents are removed by boiling with'water. For the purpose of further purification the product may be recrystallized from aqueous Ipyridin'e, whereby ltd-di- (para toluene sulfonamidm -'2;--('3-.-pyrenoyl) anthraquinone is obtained in the form of a brown crystalline powder.

17 parts of 1:4 --di (para-toluene sulfonamido) 2-(3'-pyrenoyl)-anthraquinone are hydrolyzed in 150 parts of hydrofluoric acid (99 per cent. strength) by stirring for '10 hours at 0-5 C. The 1 :4-diamino-2- (3'-pyrenoyl) -anthraquinone is precipitated by the addition'of ice and water,

Table Anthraquinonc compo- Acid component 1 Dyeing on 7 nent 2 Mols M01 cotton at l 1:4-diamino-2-(para- 4:4*-azoben zene 'digrey green.

chlorobenzoyD-ancarboxylic acid. thraquinone.

2 do 3:3-azobenzene direddish blue. olive-green.

carboxylic acid.

3 do 2:6-naphtha1ene dido grey-blue.

carboxylic acid.

4 do thianthrene dicar- .do grey;

boxylic acid of the composition used in U. 5. Patent No. 2,338,516. 5 do 2:6-benzanthrone r e ddi s h olive-green.

dicarboxylic acid. b l u e 6 do 2:8-chrysene dicarviolet grey Do.

- boxylic acid. 7 1:4-diami11o2-benzofluoranthene-dicarbluish grey" green.

ylanthraquinone. boxylic acid (see Example 1).

8 1:4-diami11o-2-parado grey blue-green.

toluyl-anthraquinone.

9.--" l:4-diamii10-2-anisoyld0 do green.

anthraquinone.

l0 l:4-diamino-2-11aph- -.do blue-grey... dull green.

thoylanthraquinone.

11 do 3:3-azobenzcne diblue green-olive.

carboxylic acid.

12 1:4-dian1ino-2-(3-pyre- 4:4-azobenzene digrey olive-green.

noyD-anthraquinone. carboxylic acid.

1:4 diamino 2-(3'-pyrenoyl) -anthraquinone may be prepared as follows:

(11) 55 parts of aluminum chloride are slowly introduced at -50 C., While stirring, into a mixture of 34 parts of l:-dichloranthraquinone- 2-carboxylic acid chloride, 20 parts of pyrene and 250 parts of ortho-dichlorobenzene. The whole is stirred for 2 hours at i0-50 0., and then for a further hour at 60-65 C. The reaction product is then decomposed With ice and hydrochloric acid, and the solvent is removed-by steam distillation. The radical is separatedby filtration, and unreacted 1z4-dichloranthraquinone-2-carboxylic acid is extracted therefrom by means of a dilute solution of sodium carbonate. There are obtained 47=parts of 1:4-dichloro-2-(3'-pyrenoyl)- anthraquinone in the form of a brown .powder which melts at 249 C. (uncorrected) after. recrystallisation from ortho-dichlorobenzene.

(b) A mixture of I5 parts of 1:4-dichloro-2- (3'-pyrenoyl) -anthraquinone, 1 i0.parts of para- 7 1 :4 diamino-2 -naphthoyl-anthraquinone may be prepared as follows:

81 parts of aluminum chloride are introduced, While stirring, into a solution at 40-45" C. of 69 parts of 1:4-dichloranthraquinone-2-carboxylic acid chloride in a mixture of 150 parts each of ortho-dichlorobenzene and naphthalene. The whole is stirred for 1 hour at 40-45 C. and for a further hour at 60-7 0., and the product is then worked up as described under (a) above. chloro-2-naphthoyl-anthraquinone melts at 214 C. (uncorrected) after repeated recrystallization from ortho-dichlorobenzene and toluene. The 1z4-dichloro-2-naphthoyl-anthraquinone is further reacted as described under (1)) and (0) above, and 1:4-diamino-2-naphthoyl-anthraquinone is obtained. It crystallizes from orthodichlorobenzene in the form of blue crystals.

EXAMPLE 5 1.5 parts of the vat dyestufi obtained as described in Example l'are vatted with 6 parts by volume of caustic soda solution of 36 B. and 3 parts of sodium hydrosulfite at about 50 C. in 300 parts of water. The stock vatso prepared is added to a dyebath containing in 1700 parts of water 4 parts by volume of caustic soda solution of 36 B. and 2 parts of sodium hydrosulfite, and then 100 parts of cotton are entered at 40 C.

After minutes parts of sodium chloride are added and dyeing is continued for 1 hour and 40-50 C. The cotton is then squeezed, oxidized in the air, rinsed, acidified and again rinsed and, if desired, soaped at the boil. The cotton is dyed a fast grey tint.

0 NH ll 0 0-K; C 0 NH (I? 7 0 0 R30 0@ l What I claim is:

1. A vat dyestufi of the" general formula 0 NH; NH; 0

I I H C C0-R1 RaCO-C@ I NH-C o-n,-o O-NH I wherein R1 and R3 stand for an aryl radical each end wherein -CO'--R2-CO- stands for the radical of an aromatic dicarboxylic acid ofthe formula HOOCR2COOI-I.

2. A vat dyestufi of the general formula 0 NH2 N11, 0

1] -O l I l N; t

wherein R1 and Rs stand for an aryl radical each.

4. A vat dyestufi of the general formula 00 NH O wherein each R stands for a halogen phenyl radical.

5. A vat dyestufi of the general formula NH; Cl)

9? 10 wherein each R stands for a halogenphenyl radical.

6. A vat dyestuff of the general formula '0 NH: FH: O

wherein each R standsfor a, halogenphenyl radical.

7. The vat dyestuff of the formula O NHz II I -0o-C -c1 CO-NH II NH 00 8. The vat dyestuff of the formula 0 NE: NH, 0

II I I COC O1 C1 C O0 I NH-O 0 C -C c0 NH I 9. The vat dyestufi of the formula.

0 NH, NEE 0 QFW CI ol co g' l 10. The vat dyestuff of the formula 11 12 11. The vat dyestuff of the formula,

O NH;

EDUARD MOERGELI.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS 

1. A VAT DYESTUFF OF THE GENERAL FORMULA 